Sulphuric reaction products of aliphatic hydroxy carboxylic acids



the, production of Patented July 9, 1935 SULPHURIC REACTION PRODUCTS rna'nc rmmoxr Heinrich Bertsch, Chemnitz, to the firm 11. Th. Biihme Chemnitz, Germany GARBOXYLIC ACIDS OF ALI- Germany, assignor Aktiengesellschaft,

' No Drawing. Application March 12, 1931, Serial No. 522,169. In Germany March 13, 1930 1 Claims. (0!. 260-99-12) This invention relates to processes of preparing sulphated oils adapted as wetting'or moistenin agents.

More particularly the v such agents by sulphating higher aliphatic hydroxy-polycarboxylic acid derivatives, said derivatives being derived from said acid by reducing one or more of said carboxyl groups to aCI-IaOI-I- group and esterifying the remaining carboxyl groups either before or after the reduction step with alcohol residues.

According to'known'processes of making sulphonated, oils for this use, fatty acids or their glycerides are converted into water-soluble sulpartially reduced and the phonic acid compounds by the action of a suiphonating agent upon either the unsaturated carbon atoms or thehydroxyl groups of the fatty com? pounds. It has also been proposed to use, instead of carboxyiic acids, the corresponding higher aliphatic mono-hydroxyalcohols as the initial material for the sulphonation. It was found that the sulphonates of these compounds, due to the absence of carboxyl groups, are non-sensitive to calcium and magnesium salts present in hard water and are noteworthy because of their very good softening and smoothingproperties.

Furthermore, it has been proposed to employ fatty acids esterified'with aliphatic, hydro-are matic, or-aromatic alcohols or with phenols as the initial material for the preparation of the sulphonated oils, with the result that the products made therefrom are many .times more emcient as moisteningagents than the agents made from free fatty acids or their glycerides.

' The products prepared according to the method of the present invention are extremely valuable in possessing theggoodproperties of both of the above described sulphonated oil products.

In proceeding in accordance with the invention, certain derivatives ,of higher aliphatic dicarboxyiic or poly-carboxylic .acids are sulphated. The acids from which the derivatives are formed may be prepared by reacting a halogen hydrid with higher aliphatic unsaturated compounds,'for example, unsaturated fatty acids, converting the resulting halogen hydride addi tion product by means of potassium cyanide and saponifying the nitriles formed, intopolybasic pr ucing the derivatives, the carboxyl groups of these polybasic acids are then either quantitatively reduced to a. 'CH2OH group or only remaining ones either before or after the reduction are esterifled by the reaction of alcohols or phenols therewith. The

invention is directed to' present resulting derivative co mpounds are either higher aliphatic poly-hydroxy alcohols or esters of higher aliphatic hydroxy aci The derivatives are then sulphated in a manner known per se, the method of sulphating formin no part of the present invention.

Example 1 one hundred kilograms of the dibutyl ester made by the addition of hydrogen bromide in solution in acetic acid to.ricinoleic acid, conversion of the bromo-hydroxy-steariciacid with potassium cyanide, saponification of the nitrile and the esterification of the. resulting hydroxy dicarboxylic acid with butyl alcohol are reduced by treatment with that ethyl alcohol necessary group. For instance,

amount of sodium and the amount of these substances used is in the proportion of 4 atoms of sodium and 4 of the dibutyl ester of acid.- Thus by weight, 22 kgs.

molecules of ethyl'alcoho'l per mol.

heptadecanol dicarbcxylic of sodium and 44 kgs. of ethyl alcohol may be used, although it is obvious that the amount of these substances may be slightly in excess of The reaction product,

decandiol carboxylic adding thereto four trated sulphuric acid the, theoretical quantity. the butyl ester. of octaacid, is sulphated, as by times as much of concenat a temperature between -5 and 0 0., whereby the hydroxyl converted into sulphuric acid ester groups.

I washing this product with a saturated solution of groups are After Glaubers salt and neutralization with soda lye,-

there is obtained a product which goes into solution in water very quickly and which moistens ,very readily.

Example 2 The dibutyl ester acid prepared as desc of the hydroxy carboxylic ribed in Example 1 is reduced with-the amount of sodium and ethyl alcohol needed to react with two ester groups. For instance, the amounts may be .in the propor- "tionof 8 atoms of sodium 1 mol. of the dibutyl ester of ethyl alcohol to and 8 molecules of heptadecanol dicarboxylic acid. The reduction maybe aided by treatment with hydrogen under pressure. The product" formed'is'an eicosantrlol which upon sulphation in accordance with known methods yields preparations which have, to an increased degree, the advantageous properties of thesulphonates of fatty alcohols previously described.

vention are especially to react with one ester prising esterii'ying high solubility in water, high moistening power, and-their resistance to acids. These qualities are thought due at least in part to the larger number of sulphated hydroiwl groups and the introduction of ester groups. Their stability against calcium and magnesium salts is very good because of the absence oi! tree carboxyl groups.

Having thus described my invention, what is claimed as new and desired to beseeured by Letters Patent is:

1. The process oi. preparing sulphated oils comprising sulphating a higher aliphatic.hydroxy-polycarboxylic acid derivative compound having more than 8 carbon atoms, said compound being a derivative of an acid of the described character in which at least one carboxyl group sisting of phenols and mon'ohydroxy alcohols.

sulting product.

- ing more than consisting of phenols and nionohydroxy alcohols, then reducing at least one of the ester groups to a CHzOH group, and finally sulphating the re- 4. The process of preparing sulphated oils comprising reducing the carboxylic groups of a higher aliphatic hydroxy-polycarboxylic acid hav- 8 carbon atoms to CHQOH groups and sulphating the resulting product. 5.' The process of preparing sulphated oils comprising sulphating a higher aliphatic compound of the general formula wherein X is H or lower alkyl or phenyl, k is an integer or zero, m and n are integers, k+m is at least 2, and lc+m+n is more than 8.

6. The process of preparing sulphated oils comprising esterifying .a higher aliphatic hydroxypolycarboxylic acid having morethan 8 carbon atoms by a compound selected from the group consisting of phenols and monohydroxy alcohols and reducing at least one group COOX, wherein X is H or lower alkyl or phenyl to a group CHzOH, and sulphating the resulting product.

7. A dispersing agent comprising in substantial quantity a sulphuric acid ester of a higher aliphatic compound of the. general formula wherein X is H or lower alkyl or phenyl, k is an 

